Production of morpholine vinyl ethers and related compounds



;;; 21 Claims. (Cl. 260-28) ence of an aqueous solution, or of a suitable volpoint of 210 C. Another fraction of the ben- 10 thereof thus produced may then be recovered in ammonia is morpholine as indicated in the equaa number of ways hereinafter indicated. tion:

The reaction mixture must be maintained alkaline during the first step of the process, either by (hm-'01 the use of an excess of ammoniacal solution, an O +3NH; O NH+2NH4C1 "2'0 excess of morpholine with or without diluent, or,

vinyl ether or homologue thereof, a strong base /C|H4\ otnloi 25 such as sodium hydroxide is required.

When in the process, ,Bfi' dichlorodiethyl ether, NEH-O NH+O i. e. bis-beta-chlorethyl ether, is the dihalo- I genated ether utilized, there is produced N mor- C2H4 02H; pholine 2-ethyl vinyl ether, as a final product. \O+NH4O1 30 The latter is a mobile, mildly odorous, colorless V I\ liquid having a boiling point of 209 to 211 c., and a specific gravity of 1.00 at 20 C. It is com- N-bis morpholinium chloride. pletely miscible with water and paraffin oil, and Treatment of this amine chloride with caustic -3 it is strongly basic. soda or similar strong base produces:

The process is illustrated by the following examplesz I C2H4 C2H4 Example 1 40 1850 grams of 6p dichlorodiethyl ether, and 40 12,700 grams aqueous ammonia, giving a molar CiHt E 01114 UNITED STATES PATENT OFFICE PRODUCTION OF MORPHOLINE VINYL ETHERS AND RELATED COMPOUNDS Alexander L. Wilson, Pittsburgh, Pa., assignor, by mesne assignments, to Union Carbide and Carbon Corporation, a corporation of New York No Drawing. Application July 19, 1934, Serial No. 736,041

I This invention relates tothe vinyl alkyl ethers the intermediate N-bis morpholinium chloride to of morpholine; and their homologues and related form the corresponding hydroxide. The resultcompounds; and'to a process of making the same. ant solution was extracted with benzene in the 7 The process involves reacting together a pfidicold for isolating the free amines. The benzene '5 halogenated dialkyl ether with morpholine, a extract was then distilled, and the fraction dis- 5 substituted morpholine, or with a mixtureof the tilling over between 198208 C. was separately saidether and an excess of ammonia whichinterrecovered. This fraction was very rich in the act to form morpholine or a homologue thereof. N morpholine 2-ethyl vinyl ether, which is puri- The reactionpreferably is conducted in the presfied by redistillation, and. which has a boiling I atile solvent such as methanol. The resultant zene extract contains substantial amounts of reaction products are then reacted with an aquemorpholine.

ous solution of a fixed alkali, such as caustic soda. It seems probable that the primary reaction The morpholine vinyl ether or homologues product of ,Bfi dichloro-di-ethyl ether. and the as in the'reaction of morpholine with dichloroisopropyl ether, by caustic alkali. For the decomposition of the dimorpholinium chloride or intermediate product, to produce the morpholine This then reacts with another molecule of the dichlordiethyl ether and ammonia to form the spirocyclic quaternary amine chloride:

ratio of 14 of ammonia to 1 of ether, were reacted in an autoclave at 50-55 C. for 80 hours with constant agitation. The reaction products were then distilled to remove unreacted dichlordiethyl N, 2 morpholinium hydroxide, which readily decomposes to form N morpholine 2-ethy1 vinyl ether, having the probable formula:

ether and water, thus concentrating the product 0,11, 45 to the point where ammonium chloride produced H o H in the reaction precipitated. This with small CH C amounts of iron oxide presentwere then reso moved by filtration The'filtrate was then The time required for the initial reaction with ther concentrated. to the SatUIatiOII pointof the ammonia may be greatly reduced increasing 1 boili solution- Upon cooling the solution the somewhat the temperature at which the reaction mass partly solidified. This residue was then is conducted. Moreover, under certain conditreated with strong aqueous causticsoda solution tions the step of solvent extraction of the initial in excess of the amount required'to react with reaction residues is unnecessary. 55

then bejcentrifuged to remove the precipitated salt. Theresidual liquor separates into an Example 2 v A high yield of N morpholine Z-ethyl vinyl ether has been secured by reacting together for four hours in an autoclave, 95 parts by weight of ,85' dichlordiethyl ether and 107 parts of anhydrous ammoniain 2'78 parts of: water. This reaction was conducted at 55 pounds per square inch pressure, and the temperature rose from 75 to 90 C. during the reaction.

liquor was treated with an excess of aqueous solution of caustic soda and the resultant mixture distilled to 124 C. The distillate resulting. from the continued distillation of the caustic solution contains the 'rnorpholine vinyl ether, together with-morpholine,,water'and ammonia; and most of the morpholine 'vinyl'ether is recovered therefrom by fractional distillation, fractional condensation, or by other means.

- The stillresidue may be allowed to settle, and

aqueous-caustic layer and a supernatant amine layer. boiledto 128 C., and a further quantity of salt and an amine layer are removed.

Some morpholine ethyl vinyl ether is present in the distillate obtained during concentration of the mixture from the caustic treatment; and

may be-recovered by fractional distillation or other suitable treatment.

' mately one-third of the said ether was present in 7 this way undue rise in temperature is prevented.

this caustic layer. The caustic solution, or the residuethereof after an extraction with benzene or the like, can be used again in the process. The liquid amine layer or layers generally contain the major part or the morpholine vinyl ether produced, which is recovered therefrom by any suitable method, as by fractional distillation.

'Frequently it is desirable toconduct the reaction between the m6 dichlordiethyl ether and ammonia in a solution of a volatile solvent which is chemically inert to the reactants. This is particularly desirable'iorcontrolling the rate of reaction and the temperature in the mass 'of, reactants where the mixture is-initially heated to temperatures as highas' "C. or higher. In

A'solvent having a high absorptive capacity for ammonia, such as methanol, is very satisfactory for the purpose.

n I Example 3 V s I In one instance', a solution of 300 grams of 3p dichlordiethyl 'ether,"1'70 grams anhydrous am-.

monia, 2400 c. c. methanol, and '5 grams cuprous chloride were heated in an autoclave for 25 hours at 100-110 C. The excess of ammonia then was evaporated, and methanol was added in amount sufficienttodissolve the amine salts. This solu- .tion was then treated with sodium hydroxide, and

The molar: 'ratioof ammonia to dichlordiethyl etherwas 10 The former is returned to the still and 'jlogueof morpholine ethyl vinyl ether.

pholine ethyl vinyl ether was recovered by redistillation of the fraction boiling within the range 180-215 C; at atmospheric pressure.

While it is preferred in the practice of the process to utilize molarratios of ammonia to Q5 dichlordiethyl ether of around 4.or 5:1, other 'ratios within' the range iof ifrcm 2-zlrto120:1 and. higher.have-beenlsuccessfullyemployed, and sat; f

isfactory yields of morpholine ethyl vinyl ether secured. The use of a catalyst in the process is H The dimorpholinium chloride or homologue" may be'recovered directly from the reaction mixture resulting from the ammonia or morpholine treatment of the said ether. According to'one,

procedure for recovering the intermediate chloride, the said reaction mixture was treated with sodium hydroxide or its equivalent in amount less than that needed to neutralize the solutionand to convert the dimo-rpholinium chloride to the corresponding .;hydroxide. All excess, ammonia,

chlo ride was obtained from lthe alcohol extract by recrystallization. 1 r

pimprphou um chloride is' very stable, and is It 'forms colorless ,cr'ystals'i. Upon. heating, it darkensso'rnewhat around 280 Cl andmelts with very soluble 'in water and 'in the lower' alcohols.

decomposition near 300C. Upon treatment with aqueous sodium hydroxideit forms a supernatant colored oilylayer which is not soluble inbenzene and is evidentlyan impure dimorpholinium hydroxideg, On. heating the caustic solution to over 100 C. this layer is gradually convertedtomorpholine vinyl'ether, and becomes soluble in benzene. 1 H 7, j t

The process of the invention is also adapted'for s the production-of vinyl ethyl ethers and homologous, ethers 'of the various homologues of.

morpholine, as for example, by the ammonia treatment in the manner described, of various B5 dihalogenated dialkyl ethers, such as 55f dichlor-di isopropylether, or' by the morpholine treatment of the same ether.

- Upon reacting pp dichlor-di-isopropyl ether withammonia in manner similar to the treatment of the vdichlor diethyl ether in the examples supra a product has beensecured having properties similar to those of krnorpholine 2 -ethyl vinyl ether, which is evident-lythe tetramethyl homo- 7 Mixed .homologues, such as the reaction products of morpholine -and cc dichlor-di-isopro'pyl ether, and

of dimethyl. morpholine with cc dichlordiethyl ether, likewise may be produced by the process; 7

7 Eimmplee s w 7 :11-10 parts by weight of B5 dichlor di-isopropyl ether and 3890 parts by weight of aqueous 28% ture of from 90;to C. The reaction product was concentratedby distillation; and unreacted ammonia were heated in a'n autoclave for'six'days; 1 I

with a total time of about 30 hours ata temperaexcess-of sodium hydroxide and Was evaporated,

some oi the resultant amines being carriedinto the aqueous distillate, and some separatingin the still as a supernatant layeriovera residue of caustie and brine. l-Separaticn and distillation of the from 120 to 2 30.C. Fractionaldistillation there amines yieldeda fractionboilingin the range of.

. 1 ether.

whichwas evidently dimethyl morpholine; and a fraction boiling at 230 to 240 C. which evidently was dimethyl morpholine isopropyl isopropenyl ether. This compound apparently has a structure corresponding to the formula (IJHa The last-named propylene homologue of morpholine ethyl vinyl other is a colorless mobile liquid having the peculiar fiat odor of morpholine ethyl vinyl ether. It is practically insoluble in water, but is a fairly strong base. It is completely miscible with methyl alcohol and with diethyl 7 Example 5 y 86 parts of [35' dichlor-di-isopropyl"ether, 43

parts of morpholine, 20 parts of sodium hydroxide,

and'20 parts of water, all parts by weight, were reacted (refluxed) for 15 hours at the boiling point of the mixture, or approximately 100 C. The resultant reaction products were then diluted with water and distilled to remove the unreacted ether and morpholine by steam distillation. The residue was extracted with isopropanol, and the extract was filtered to remove the insoluble sodium chloride. Dimethyl dimorpholinium chloride was then obtained by crystallization from this isopropanol solution of the amine chlorides.

The former is a white, high-melting, stable solid, soluble in water and in alcohols. Heating this chloride with sodium hydroxide in alcohol yields an amine corresponding to a dimethyl derivative of morpholine ethyl vinyl ether, in the form of a colorless, mobile liquid, boiling at 215-225 C., soluble in alcohols, slightly soluble in water, and strongly basic. The formula of this dimethyl morpholine ethyl vinyl ether may be written as follows:

That fraction of the benzene extract recited in Example 1 which upon distillation boils within the range from about 126 C. to about 180 0. contains substantial amounts of morpholine, formed by the ammonia treatment of the cc dihalogenated di-ethyl ether. Preferably such fraction is recycled and reused in the process for the production of the morpholine ethyl vinyl ether- Many low-boiling volatile solvents other than isopropyl ether and benzene can be utilized in the extraction of the amines from the mixture resulting from the caustic alkali treatment. These solvents should be chemically inert with respect to the materials of the process, and should be substantially immiscible with water.

However, because of the difficulties met in separating these amines from water by distillation, it is generally preferred to avoid such solvent extraction, and to partially evaporate r concentrate the primary reaction mixture from the morpholine or ammonia treatment of the ether, thereafter partially neutralize the solution with sodium hydroxide, and evaporate further to remove combined ammonia and water. An excess of sodium hydroxide is then added, and the mixture is refluxed until the dimorpholinium hydroxide is completely decomposed with the formation of amines, which are then separated by gravity as an amine layer. The latter is fractionally distilled to recover the various amines present.

The reaction between the dihalogenated ether and ammonia may be carried out at pressures around atmospheric, but for the most efiicient operation low superatmospheric pressures are preferred; and pressures around 50 to 55 pounds per square inch gauge have been uniformly satisfactory.

It will be seen from the foregoing description that the invention in its broader scope embraces the production of morpholine substituted vinyl ethers which in general are mobile, mediumor high-boiling liquids having structures corresponding to the general formula wherein Y, Y Y and Y respectively, may represent an atom of hydrogen or an alkyl radical; X may represent a saturated alkyl residue; and X2 may represent an unsaturated alkyl residue.

I claim:

1. As a chemical compound, N morpholine 2- ethyl vinyl ether, the same being a mobile, colorless liquid having a boiling point of arr-211 (3., and a specific gravity of 1.00 at 20 C.

2. As a chemical compound, dimethyl morpholine isopropyl isopropenyl ether, the same being a colorless mobile liquid having a boiling range of from about 230 C. to about 240 C., practically insoluble in water, completely miscible with methyl alcohol and with diethyl ether, and being a fairly strong base.

3. As a chemical compound, dimethyl morpholine ethyl vinyl ether, the same being a colorless, strongly basic liquid boiling at from 215 C. to 225 C., soluble in alcohols, and slightly soluble in water.

4. In the process of making a morpholine alkyl vinyl ether, the step which comprises reacting a morpholine with a BB dihalogenated di-alkyl ether while maintaining the reaction mixture alkaline.

5. In the process of making a morpholine substituted ethyl vinyl ether, the step which comprises reacting morpholine with a dialkyl substituted e dichlor-di-ethyl ether in an alkaline medium.

6. In the process of making a morpholine substituted ethyl vinyl ether, the step which comprises reacting a dialkyl substituted morpholine with ,8/3' dichlor-di-ethyl ether in an alkaline medium.

7. The process of making morpholine ethyl vinyl ether, which comprises reacting morpholine in alkaline solution with ,8/3 dihalogenated di-ethyl ether, treating the resultant reaction mixture with an excess of a caustic alkali, and recovering the N morpholine 2-ethyl vinyl ether thus produced.

8. The process of making morpholine ethyl vinyl ether, which comprises reacting a [35' dihalogenated di-ethyl ether with ammonia in a molar V latter, and separately recovering the. fraction con ratioof at least 2 o'f-ammonia tol of the ether in the presence of an'aqueous alkaline solution, treating the reaction mixture with an aqueous caustic alkali solution, fractionally distilling the resultant reaction mixture,'and separately recovtaining the morpholine alkyl vinyl ether.

solution, concentrating the resultant mixture, fractionally distilling the latter, and separately recovering a fraction distilling over within the a range 180-215 C. and containing the morpho- 10. The process of making morpholine ethyl vinyl ether,which comprises reacting a fie" dichlor-di-ethyl ether with ammonia in a molar ratioof at least 4 of ammonia to 1. of theether in aqueous alkaline solution, treating the reaction mixture with an excess of aqueous caustic alkali line ethyl vinyl ether. r 7

11. The process of making a morpholine substituted alkylvinyl ether, which comprises reacting on dichlor-di-isopropyl ether with ammonia in a molar ratio of at least 3 mols of ammonia to 1 mol of the ether in the presence of an alkaline solution, treating the resultant reaction mixture with an excess of a strong alkali, and'recovering the substituted morpholine vinyl ether thus produced. V

12. In the process of making a morpholine substituted alkyl vinyl ether, the step which comprises reacting [35. dichlor-diqsopropyl" ether with ammonia in a molar ratio of at least 5 of ammonia to 1 of the said ether.

13. The process of making a morpholine alkyl vinyl ether, which comprises reacting under pressure a [35 dihalogenated dialkyl ether with ammonia in a molarratio of at least '5 of ammonia to 1 of the dihalogenated ether, treating the resultant mixture with an excess of a caustic alkali, and recovering the morpholine alkyl vinyl ether thus produced.

14. The process of making morpholine ethyl vinyl. ether, which comprises reacting fie" di chlor-di-ethyl ether with ammonia ina molar ratio of at least 5 of ammonia to 1 of the (1111310!- genated ether, concentrating the mixture, treating the resultant mixture with an aqueous solution of caustic alkali, thereby forming morphoe line ethyl vinyl ether, stratifying the mixture into a plurality of layers including an amine layer and an aqueous caustic layer, separating the above-mentioned layers, separately fractionally distilling the amine layer and the caustic layer, and separately recovering the fractions of the respective layers distilling within the range 186 215? C. at atmospheric pressme.

15. In the process of producing a morpholinesubstituted alkyl vinyl ether, the steps which comprise reacting in an alkalinemedium a morpholine with a 5,8 dihalogenated dialkyl ether,

treating the resultant reaction product with an excess of a caustic alkali, and recovering the morpholine-substituted alkyl vinyl ether thus produced. 1 V V 16. The process of making a morpholine-substituted alkyl vinyl ether, which comprises re:

acting with ammonia an ether selected from'the group thereof consisting of BB 'dihalogenated;

diethyl ether and 5,8 dihalogenated di-isopropyl ether, in a molecular ratio of at least3' mols of ammonia to 1 mol of the ether, in the presence I of 'an. alkaline solution, treating the resultant reaction mixture with-an excess of a strong alkali, and recovering the morpholine-substituted ether thus produced. 7 V a 17. The process of, making a morpholine alkyl vinyl ether, whlch'comprises .reactinga' /SB' di- 7 ether, while maintaining the reaction mixture alkaline," treating the .resultantreaction mixture 1 with an excess of an aqueous c austic alkali solue tion, thereby producing a morpholine alkyl vinyl} etheiyand recovering the latter. 7

'18.. The process of: making morpholine ethyl 'halfogenated dialkyl ether withiammonia in a l molarjr'atio of at 'leastfil of ammonia to 1 of the .20 1.

vinyl ether, which comprises reacting-pip dichlor-di-ethyl ether With ammoniain a molar ratio of at least 4 of ammonia to -1 of the ether, in aqueous alkaline solution, treating thereaction mixture with an excess of aqueouscaustic alkali, concentrating the resultant mixture thereby separating it into a plurality of layers including a layer of caustic liquor, further concentrat ing the last-namedlayer, separating from the concentrated liquor the amine layer containing the morpholine ethyl, vinyl ether thusformed,

fractionally distilling theamine layer, and separately recovering the fraction boiling at 209 to 211 C. at atmospheric pressure.

19. In the process of producing a morpholine alkyl vinyl ether, the stepwhich comprises reacting a morpholine'with a [35' dihalogenated dialkyl ether in solution in a volatile organic solvent which is chemically inert to the reactants, while maintaining the reaction mixture alkaline.

20. A-morpholine-substituted alkyl vinyl ether, 7

the same being a mobile liquid having a structure corresponding to the general formula wherein Y1, Y2, Y3 and'Yi respectively represent v saturated alkyl radicals and hydrogen. 7

, 21. The process of making a morpholine alkyl vinyl ether, which comprises reacting a 35' radicals selected from the' group consisting of dihalogenat'ed dialkyl ether with ammonia m i molar ratio of at leasttwo of, ammonia to one of the ether while maintaining the reaction mix ture alkaline, thereby intermediately' forming a morpholine which reacts with additional BB dihalogenated dialkyl ether, treating the resultant reaction mixture with an excess of an aqueous caustic alkali solution, thereby producing a morpholine alkyl vinyl ether, and recovering the latter.

ALEXANDER. L. WILSON, 

